Nitrated and/or fluorinated ethyl amino acetic acids and esters thereof

ABSTRACT

1. A COMPOUND OF THE FORMULA   (X-C(-NO2)2-CH2)2-N-CH2-COO-CH2-C(-NO2)2-X&#39;&#39;   WHEREIN X AND X&#39;&#39; VRY INDEPNDENTLY AND ARE SELECTED FROM THE GROUP CONSISTING OF F, NO2, CH3, AND H.

United States. Patent ABSTRACT OF THE DISCLOSURE Compounds of the formula NO: NO: X-i oH,-Norr,-Coom-iJ-x' 1 102 ,2 1 N02 where X and X' vary independently and represent F,

N0 CH and H, are prepared by contacting an alcohol of the formula x'- CHIOH with an acid chloride of the formula The compounds of this invention find use as plasticizers and energetic additives in explosive compositions.

BACKGROUND OF THE INVENTION This invention relates generally to chemical compounds and more particularly to carboxylic acid esters which find use as plasticizers and energetic additives in explosive compositions.

In order to be considered a good plasticizer in an explosive composition, a compound must not only have the ability to act as a plasticizer but must also have a low volatility, good thermal stability and be capable of re1easing a relatively large amount of energy upon detonation. The low volatility is required in order to avoid vaporization of the plasticizer after it is mixed into an explosve composition which may remain unused for a relatively long period of time. If it should evaporate to any great extent, one would lose a portion of the beneficial properties realized by using a plasticizer in an explosive composition. Similarly, if it is not thermally stable, the plasticizer will decompose and again one would lose part of the beneficial properties realized by using a plasticizer in an explosive composition. Finally, it is important for the plasticizer to release a relative large amount of energy on detonation so that one can obtain maximum energy release per unit weight of explosive composition. In thls respect these compounds can also be used as energetic additives to explosive compositions in order to increase the energy yield upon detonation.

Thus continuing research is conducted to find compounds which are highly energetic, have low volatility and which are thermally stable.

SUMMARY OF THE INVENTION Accordingly, one object of this invention is to provide carboxylic acid esters.

Another object of this invention is to provide carboxylic acid esters which can be used as plasticizers in explosive compositions.

"ice

Another object of this invention is to provide carboxylic acid esters which have a relatively low volatility.

A further object of this invention is to provide carboxylic acid esters which have relatively good thermal stability.

A still further obiect of this invention is to provide carboxylic acid esters which have relatively high energy.

These and other objects of this invention are accomplished by providing compounds of the formula N02 N02 (x-ooH2--NoH2-C0oH2-iJ-X' N02 /2 i N02 where X and X vary independently and are selected from the group consisting of F, N0 CH and H, which are prepared by contacting an alcohol of the formula N 02 JU-i'J-CHzOH with an acid chloride of the formula DESCRIPTION OF THE PREFERRED EMBODIMENT The carboxylic acid esters of this invention are prepared by any of the conventional esterification techniques such as, for example, contacting an acid chloride of the with an alcohol of the formula under the typical known techniques. The above acid chloride is obtained by reacting the corresponding carboxylic acid with a conventional reagent such as thionyl chloride under prior art conditions. The acid is obtained merely by hydrolysis of the corresponding ethyl ester, again under conventional conditions. The preparation of the ethyl esters is outlined and disclosed in patent application entitled Chemical," Ser. No. 110,628, by William H. Gilligan filed on the same date herewith and hereby incorporated by reference.

The general nature of the invention having been set forth, the following examples are presented as specific illustrations thereof. It will be understood that the invention is not limited to these specific examples but is susceptible to various modifications that will be recognized by one of ordinary skill in the art.

EXAMPLE I N,N-bis (2-fluoro-2,2-dinitroethyl) glycine A solution of 2.55 g. (6.8 mmole) of ethyl N,N-bis(2- fluoro-2,2-dinitroethyl) aminoacetate, the preparation of which is disclosed in patent application entitled Chemical, Ser. No. 110,628, by William H. Gilligian, filed on the same day herewith in 10 m1. of trifluoroacetic acid and 4 m1. of 6N hydrochloric acid was refluxed for 8 hours. After cooling, the solvents were removed in vacuo and the product was recrystallized from meth- 3 ylene chloride to give 2.14 g. of N,N-bis(2-fluoro-2,2- dinitroethyl)aminoacetic acid, m.p. 140-152" C.

EXAMPLE II 2-fiuoro-2,2-dinitroethyl N,N-bis(2-fluoro-2,2-

dinitroethyl) aminoacetate A few drops of pyridine and 0.5 m1. of thionyl chloride were added to a solution of 1.0 g. (2.9 mmole) of N,N-bis(fiuorodinitroethyl) aminoacetic acid in 5 ml. of ethylene chloride. The solution was gradually heated to 90 C. allowed to cool and the volatiles removed by evaporation in vacuo. The resulting crude acyl chloride was dissolved in 5 m1. of methylene chloride and 0.4 ml. of 2-fiuoro-2,2-dinitroethanol was added. The solution of the reactants was cooled in an ice-bath and 0.3 ml. of pyridine was added, dropwise with stirring. The solution was allowed to warm to ambient temperature and then refluxed for 1 hour. The reaction mixture was then taken up in 50 ml. of methylene chloride and washed successively with dilute HCl, water and 0.1N sodium hydroxide. After drying with anhydrous magnesium sulfate, the solvent was evaporated to give 1.22 g. of 2-fiuoro 2,2 dinitroethyl N,N-bis(2-fluoro-2,2-dinitroethyl) aminoacetate.

Similarly, when compounds wherein both X and X' have different values, one merely uses the corresponding starting materials in the above procedures.

Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described herein.

secured by wherein X and X vary independently and are selected from the group consisting of F, N0 CH and H.

2. The compound of claim 1 wherein X and X are the same.

3. The compound of claim 2 wherein both X and X are F.

4. A compound of the formula wherein X is selected from the group consisting of F, N0 CH and H.

5. The compound of claim 4 wherein X is F.

References Cited UNITED STATES PATENTS 6/1960 Klager 14992 X 4/1971 Frankel 149--92 X LELAND A. SEBASTIAN, Primary Examiner US. Cl. X.R. 

1. A COMPOUND OF THE FORMULA 